Method of producing press-hardened and coated steel parts at a high productivity rate

ABSTRACT

A sheet or blank is provided which includes a substrate and pre-coating on at least one face of the substrate. A polymerized layer overlies at least a part of the pre-coating and has a thickness from 2 μm to 30 μm, a nitrogen content of less than 1% by weight, carbon pigments in a quantity from 3 to 30% by weight and does not include a polymer with silicon. A welded blank, part and fabrication methods are also provided.

This is a Continuation of U.S. patent application Ser. No. 15/301,316,filed Sep. 30, 2016 as a National Phase Application of InternationalPatent Application PCT/IB2015/000143, filed Feb. 13, 2015 which claimspriority to International Patent Application PCT/IB2014/000455, filedMar. 31, 2014, the disclosures of which are hereby incorporated byreference herein.

This invention relates to a fabrication method for parts from pre-coatedsteel sheets that are heated, stamped and then hardened during a coolingobtained by holding in a pressing tool; these parts are intended to beused as, among other things, structural elements in automotive vehiclesto perform anti-intrusion or energy absorption functions. Parts of thistype can also be used, for example, for the fabrication of tools orparts of agricultural machinery.

BACKGROUND

In this type of applications, the objective is to produce steel partsthat combine high mechanical strength, good corrosion resistance andgood weldability. It must also be possible to fabricate these hotstamped parts using high productivity methods. These requirements applyin particular in the automobile industry, where the objective is toreduce significantly the weight of the vehicles. Anti-intrusion parts orparts that play a role in the safety of automotive vehicles such asbumpers, door reinforcements or center pillars, for example, require thequalities indicated above. These qualities can be obtained in particularthanks to steel parts, the microstructure of which is martensitic orbainitic-martensitic.

The fabrication of parts of this type is known in particular frompublications FR2780984 and FR2807447, according to which a blank cut ina steel sheet for heat treatment, pre-coated with a metal or metallicalloy, is heated in a furnace and then hot stamped. The pre-coating canbe aluminum or an aluminum alloy, zinc or zinc alloy. During the heatingin the furnace, this pre-coating alloys with the steel substrate to forma compound that provides protection of the surface of the steel againstdecarburization and the formation of scalet. This compound is suitablefor hot forming. Holding the piece in the tool after forming makes arapid cooling possible, which leads to the achievement of hardenedmicrostructures in the steel substrate, which are associated with goodmechanical characteristics of strength and hardness. This method isknown as “press hardening”.

In a method of this type, the blanks are generally heated in continuousfurnaces, whereby the blanks are moved forward in these furnaces onrollers. This phase comprises a heating step followed by a temperaturehold in the furnace, generally at around 900-950° C. The holdtemperature and the hold time are a function of, among other things, thethickness of the blanks and the type of pre-coating on the blanks. Forproductivity reasons, it is desirable to employ methods that make itpossible to shorten the step of heating in the furnace as much aspossible. In this regard, publication EP2312005 discloses a method inwhich a coil of steel with an aluminum pre-coating is provided and isthen annealed at 600-750° C. for a period of time ranging from 1 hour to200 hours. A diffusion of the iron from the substrate to the pre-coatingoccurs, to the point where a pre-alloy product is obtained. Aftercutting, these pre-alloyed blanks can be heated more rapidly, inparticular on account of the emissivity modification caused by thepre-alloying treatment. However, this method requires a prior,time-consuming annealing of the coil.

Document EP2463395 also proposes to accelerate the kinetics of theheating phase by locally reducing the reflectivity of a blank by meansof various methods: prior application of black paint, modification ofsurface roughness by shot blasting, by rolling, laser or immersionetching in an acid solution. This document also describes examples inwhich pigments in the aqueous phase or polyester/melamine based blackpaint in a solvent phase have been deposited on galvanized pre-coatings.Considering the conventional mixing rate: 90-92% polyester and 8-10%melamine (C₁₅H₃₀N₆O₆) in the paint layer after drying and a maximumpigment concentration by volume of 30%, the nitrogen content in thepaint layer used in these tests is on the order of 1.7 to 2.4%% afterdrying. However, this method completely disregards certain essentialproblems linked to the later utilization of these parts. After hotstamping, the parts must be suitable for painting by cataphoresis, mustbe weldable and corrosion resistant. However, as will be shown below,the application of a conventional black paint that is resistant to hightemperatures before hot stamping does not make it possible to obtainthese properties.

Attempts have therefore been made to identify a method that makes itpossible to simultaneously increase the productivity of the hot stampingprocess and to control the process so that the hot stamped and hardenedparts thus obtained are compatible with conventional industrialproduction conditions, i.e. they do not require, for example, amodification of the existing settings of resistance spot weldingmachines for the assembly of these parts. This method must also becompatible with the fabrication of welded blanks pre-coated with analuminum coating that requires prior ablation of a portion of thepre-coating on the periphery of the blank, as described in documentEP2007545.

Attempts have also been made to identify a method that is relativelyinsensitive to certain potential variations of the fabricationconditions. In particular, attempts have been made to devise a method,the results of which are relatively insensitive to the preparationconditions of the pre-coated blank.

Moreover, a method is sought that will make it possible to obtainexcellent resistance to delayed cracking. It is known that presshardening makes it possible to obtain parts with extremely highmechanical strength, the microstructure of which can be sensitive tocracking due to the presence of hydrogen in the presence of stresses,for example those resulting from the cutting of the parts. Attempts havetherefore been made to define a method that does not present anyincreased risk of delayed cracking or that would even make it possibleto reduce sensitivity to this risk.

Additional attempts have been made to define a method that makes itpossible to fabricate welded blanks from sheets of different thicknessesthat would not result in a significantly different heating rate in thedifferent parts of these welded blanks.

Finally, attempts have been made to devise a method in which theconstituent steps and the physical elements make the implementation ofthe method possible without resulting in prohibitive cost increases.

SUMMARY OF THE INVENTION

Surprisingly, the inventors have shown that the problems mentioned abovecan be solved economically thanks to the deposition before hot stampingof a polymerized layer on a pre-coating comprising at least one layer ofaluminum or aluminum alloy, wherein the polymerized layer is composed ofa specific polymer containing carbon pigments in a quantity between 3and 30% by weight.

To this end, an object of the invention is a pre-coated sheet or blankcomprising a steel substrate for heat treatment 1 overlaid over at leasta portion of at least one of its main faces by a pre-coating 2comprising at least one layer of aluminum or aluminum alloy, overlaidover at least a portion of the pre-coating by a polymerized layer 3having a thickness between 2 and 30 μm composed of a polymer that doesnot contain silicon and the nitrogen content of which is less than 1% byweight expressed in relation to the layer, wherein the polymerized layercontains carbon pigments in a quantity between 3 and 30% by weight,expressed in relation to the layer.

Preferably, the elements of the polymer are selected from a listconsisting of C, H, O, N.

In one preferred embodiment, the polymerized layer is obtained from aresin in the form of a dispersion or an emulsion in aqueous phase.

According to another preferred embodiment, the polymerized layer isobtained from a resin in the form of solution in a non-aqueous solvent.

In another preferred embodiment, the polymerized layer consists of afilm that is roll bonded to the substrate.

Preferably, the polymerized layer is obtained from an acrylic typeresin.

In one preferred embodiment, the polymerized layer is obtained from anepoxy or acrylic type resin in the form of solution in a non-aqueoussolvent.

In another preferred embodiment, the polymerized layer consists of apolyethylene terephthalate or polyethylene or polybutylene-terephthalateor polypropylene film.

The pigments are constituted preferably at least partly of activatedcarbon.

In one preferred embodiment, the pigments are constituted at leastpartly of graphite.

The quantity of activated carbon in the polymerized layer is preferablyless than 5%, expressed by weight in relation to the layer.

Preferably, the aluminum or aluminum alloy layer constitutes more than50% of the thickness of the pre-coating.

An additional object of the invention is a sheet or a blank according toone of the embodiments described above, characterized in that thepre-coating comprises a layer of intermetallic alloy 4 in contact withthe substrate 1 overlaid by a layer of metallic aluminum alloy 5 and inthat, on at least one pre-coated surface of the sheet, the polymerizedlayer and the metallic alloy layer are not present in a zone 6, whereinthis zone is located on the periphery of the sheet or of the blank.

An additional object of the invention is a welded blank obtained bywelding at least two blanks, wherein at least one of the blanks 7 is ablank according to any one of the above characteristics having athickness e₇, and at least one of the blanks is a blank 8 having athickness e₈ constituted by a steel substrate coated by a layer ofaluminum or aluminum alloy identical to that of the blank 7, wherein thethickness of the blanks 7 and 8 is such that

$\frac{e_{7}}{e_{8}} > 1.$

The blank (7) is preferably a blank coated over the entire pre-coatingof the polymerized layer 3, and the thicknesses e₇ and e₈ are such that:

$2.6 \geq \frac{e_{7}}{e_{8}} \geq {2.2.}$

An additional object of the invention is a part 9 obtained byaustenitization, followed by hot stamping and hardening by holding inthe stamping tool, of a sheet or of a blank having a pre-coatingcomprising at least one layer of aluminum or aluminum alloy, wherein themicrostructure of the substrate 10 of the part contains martensiteand/or bainite, wherein the substrate is overlaid on at least one of itsprincipal surfaces by a coating 11 resulting from the inter-diffusionbetween the steel substrate and the pre-coating, wherein the coating 11is overlaid by a layer of oxide 12, wherein the average percentage ofoxygen by weight, between 0 and 0.01 μm below the surface of the part,is less than 25% and the average percentage of oxygen by weight, between0.1 and 0.2 μm below the surface, is less than 10%.

An additional object of the invention is a method for the fabrication ofa press-hardened part comprising the following steps in succession:

-   -   a steel sheet or blank substrate for heat treatment is provided,    -   a pre-coating is performed comprising at least one layer of        aluminum or aluminum alloy in contact with the steel substrate        on at least one of the main faces of the sheet or of the blank,        then,    -   on the pre-coating, a polymerized layer 3 is deposited having a        thickness between 2 and 30 μm, composed of a polymer that does        not contain silicon and the nitrogen content of which is less        than 1% by weight expressed in relation to the layer, wherein        the polymerized layer contains carbon pigments in a quantity        between 3 and 30% by weight, expressed in relation to the layer,        then    -   the blank or the sheet is heated to obtain an interdiffusion        between the steel substrate and the pre-coating, to obtain a        partly or completely austenitic structure on the steel, then    -   the blank or the sheet is hot stamped to obtain a part, then    -   the part is cooled by holding it in the stamping tool so that        the microstructure of the steel substrate contains, at least in        a portion of the part, martensite and/or bainite.

In one preferred embodiment, the thickness of the sheet or of the blankis between 1 and 2 mm, and the heating rate of the blank or of the sheetbetween 50 and 500° C. is between 15 and 35° C./s.

Preferably, the layer of aluminum or aluminum alloy occupies more than50% of the thickness of the pre-coating.

In one preferred embodiment, the elements of the polymer are selectedfrom a list consisting of C, H, O, N.

An additional object of the invention is a method for the fabrication ofa welded blank hot stamped and press hardened, comprising the followingsteps in succession:

-   -   a welded blank created by welding at least two blanks is        provided, comprising    -   at least one blank 7 according to one of the above        characteristics, having a thickness e₇,    -   at least one blank 8 having a thickness e₈ constituted by a        steel substrate coated with a layer of aluminum or aluminum        alloy of a pre-coating identical to that of the blank 7,    -   wherein the thickness of the blanks 7 and 8 is such that

${\frac{e_{7}}{e_{8}} > 1},$

-   -   the welded blank is heated to effect an interdiffusion between        the steel substrate and the pre-coating and to confer a partly        or totally austenitic structure on the steel, then    -   the welded blank is stamped to obtain a hot stamped welded        blank, then    -   the hot stamped welded blank is cooled by holding [it] in the        stamping tool to obtain, in at least a portion of the substrate        of the hot stamped welded blank, martensite and/or bainite.

Preferably, the welded blank, hot stamped and hardened according to theinvention is characterized in that the blank 7 is coated over the entirepre-coating, by the polymerized layer 3, and in that

$2.6 \geq \frac{e_{7}}{e_{8}} \geq {2.2.}$

BRIEF DESCRIPTION OF THE DRAWINGS

Additional characteristics and advantages of the invention will becomeapparent in the following description, which is given by way of examplewith reference to the accompanying drawings, in which:

FIG. 1 illustrates a schematic example of a pre-coated sheet or blankaccording to the invention, before hot stamping.

FIG. 2 illustrates a schematic example of a blank welded according tothe invention in which the two blanks do not have the same thickness.

FIG. 3 illustrates a schematic example of a blank according to theinvention intended to be laser welded then hot stamped.

FIG. 4 is a schematic illustration of an example of the constitution ofthe layers observed on a hot stamped piece according to the invention.

It should be noted that these diagrams do not attempt to reproduce therelative dimensions of the different constituent elements to scale.

FIG. 5 illustrates surface profile analyses of the oxygen content afterheating to 900° C., followed by hot stamping and press hardening.

FIG. 6 illustrates surface profile analyses of the carbon content, afterheating to 900° C., followed by hot stamping and press hardening.

FIG. 7 illustrates surface profile analyses of carbon, oxygen andsilicon after treatment at 900° C., followed by hot stamping and presshardening, of a pre-coated blank not according to the invention.

FIG. 9 shows the appearance of the surface of a hot stamped partaccording to the invention.

In comparison, FIG. 8 shows a hot stamped part that does not comprisethe prior deposit of a polymer layer with carbon pigments.

DETAILED DESCRIPTION

The thickness of the steel sheet used in the method according to theinvention is preferably between approximately 0.5 and 4 mm, a thicknessrange used in particular in the fabrication of structural orreinforcement parts for the automobile industry.

The steel of the substrate is a steel for heat treatment, i.e. a steelcapable of hardening after austenitization and rapid cooling byquenching.

By way of example, the steel advantageously contains the followingelements, wherein the composition is expressed in percent by weight:

A carbon content between 0.07 and 0.5%, preferably between 0.09 and0.38% by weight, and very preferably between 0.15 and 0.25% by weight.This element plays a major role in the hardenability and in themechanical strength obtained after the cooling that follows theaustenitization treatment. Below a content of 0.07% by weight, thesuitability for hardening is reduced and the mechanical tensile strengthafter press hardening is insufficient. A content of 0.15% C makes itpossible to guarantee sufficient hardenability in the most highlyhot-worked zones. Above a content of 0.5% by weight, the risk of theformation of defects increases during hardening, particularly for partswith the greatest thickness. It also becomes difficult to guaranteeductility during the bending of parts after press hardening. A carboncontent between 0.09 and 0.38% makes it possible to obtain a tensilestrength Rm between approximately 1000 and 2050 MPa when themicrostructure of the part is totally martensitic.

In addition to its deoxidizing role, manganese also has a significanteffect on hardenability in particular when it is present in quantitiesof more than 0.5% by weight, and preferably greater than 0.8% by weight.However, it is preferable to limit its addition to 3% by weight, andvery preferentially to limit it to 1.5%, to prevent excessivesegregation.

The silicon content of the steel must be between 0.02 and 0.5% byweight, and preferably between 0.1 and 0.35%. In addition to its role inthe deoxidation of the liquid steel, this element contributes to thehardening of the steel, although its concentration must be limited toprevent the excessive formation of oxides and to prevent any adverseeffect on its hot-dip coatability.

Above a concentration greater than 0.01%, chromium increaseshardenability and contributes to achieving high strength after the hotworking operation. Above a concentration equal to 1%, preferably 0.3%,the effect of chromium on the uniformity of the mechanical properties inthe part is saturated.

Aluminum is an element that promotes the oxidation and precipitation ofnitrogen. In excessive quantities, coarse aluminates are formed duringsteelmaking, which tends to reduce ductility, as a result of which thealuminum content is limited to 0.25% by weight. A minimal concentrationof 0.001% makes it possible to oxidize the steel in the liquid stateduring processing.

In excessive quantities, sulfur and phosphorus result in increasedembrittlement. That is why is preferable to limit the levels of theseelements to 0.05 and 0.1% by weight respectively.

Boron, the content of which must be between 0.0005 and 0.010% by weight,and preferably between 0.002 and 0.005% by weight, is an element thatplays an important role in terms of hardenability. Below a content of0.0005%, a sufficient effect on hardenability is not obtained. The fulleffect is obtained for a content of 0.002%. The maximum boron contentmust be less than 0.010%, and preferably 0.005%, so as not to have anadverse effect on toughness.

Titanium has a strong affinity for nitrogen. It protects the boron sothat this element is in the free form, which allows it to have its fulleffect on hardenability. Above 0.2%, however, there exists a risk offorming coarse titanium nitrides in the liquid steel, which have anegative effect on toughness. The titanium content is preferably between0.02 and 0.1%.

Optionally, the steel can also comprise tungsten in a quantity between0.001 and 0.3%% by weight. In the indicated quantities, this elementincreases hardenability and suitability for hardening thanks to theformation of carbides.

Optionally, the steel can also contain calcium in a quantity between0.0005 and 0.005%. By combining with oxygen and sulfur, calcium preventsthe formation of large inclusions, which have an undesirable effect onthe ductility of the sheets, or the parts fabricated from them.

The balance of the composition of the steel consists of iron and theunavoidable impurities resulting from processing.

Preferably, 22MnB5 steel will be used that contains, in percent byweight: 0.20-0.25% C, 1.1-1.35% Mn, 0.15-0.35% Si, 0.02-0.06% Al,0.02-0.05% Ti, 0.02-0.25% Cr, 0.002-0.004% B, the balance consisting ofiron and unavoidable impurities.

The steel substrate comprises a pre-coating of aluminum or an aluminumalloy. In the latter case, the coating therefore contains an aluminumcontent greater than 50% by weight. This pre-coating, which ispreferably applied by a continuous hot dip process, is advantageously analuminum-silicon alloy comprising 7-15% silicon by weight, 2 to 4% ironby weight, optionally between 15 and 30 ppm calcium, the remainderconsisting of aluminum and unavoidable impurities resulting fromprocessing.

The pre-coating can also be an aluminum alloy containing 40-45% Zn,3-10% Fe, 1-3% Si, the balance consisting of aluminum and theunavoidable impurities resulting from processing.

The pre-coating can also be composed of a superimposition of layersdeposited in successive steps, at least one of which layers is aluminumor an aluminum alloy. The layer of aluminum or aluminum alloy (or, ifthere are a plurality of layers of this type, the sum of the thicknessesof these layers) preferably occupies more than 50% of the thickness ofthe pre-coating.

This pre-coating is overlaid, on at least one of the main surfaces ofthe sheet, by a polymerized layer containing carbon pigments. This layercan be deposited over the totality of the metallic pre-coating or onlyon a portion of it. In this latter case, the effects conferred by thislayer, described below, are obtained in the zones where the layer ispresent. With regard in particular to the thermal effects of this layer,they also apply to a lesser extent in zones that are locally adjacent tothose in which the layer has been deposited.

This polymerized layer can in particular be obtained by the followingsteps:

-   -   starting with a resin in the form of a dispersion or an emulsion        in aqueous phase. In particular, an acrylic type resin can be        used.    -   starting with a resin in the form of solution in a non-aqueous        solvent. In particular, an epoxy type resin can be used, for        example an epoxy-phenol or acrylic resin.    -   starting with a thermoplastic polymer film roll bonded to the        substrate sheet. In particular, a polyethylene-terephthalate or        polyethylene or polybutylene-terephthalate or polypropylene film        can be used.

For reasons of productivity and regularity of thickness, this layer canpreferably be deposited by roll coating. After polymerization and/ordrying, a polymerized layer is obtained, the thickness of which isbetween 2 and 30 μm. A thickness less than 2 μm does not make itpossible to obtain a sufficient rate of coverage to implement themethod. A thickness greater than 30 μm leads to an increased risk ofcontamination of the furnaces during the subsequent heating.

The sheet or pre-coated blank is illustrated schematically in FIG. 1.FIG. 1 illustrates the steel substrate for heat treatment 1 overlaid bya metallic pre-coating 2, which is itself overlaid by a polymerizedlayer 3 containing carbon pigments.

At this stage, the steel substrate is still not hardened, i.e. it doesnot contain any constituent parts, or at least only a few constituentparts, resulting from hardening, for example less than 10% martensite.The sheet or the blank have an essentially flat shape.

In the press hardening method, the steel substrate is heated to atemperature T_(γ) that results in its austenitization, at least partly,to achieve a martensitic or bainitic transformation during thesubsequent cooling. If a sheet coated with the paint is to be heated tosuch a temperature, it would then be natural to select a paint that isresistant to a temperature T greater than T_(γ), i.e. one in which thebinder retains its function with regard to the pigments in the paint. Itis known that pigments that are resistant to high temperatures aregenerally silicone or polysiloxane resins that therefore containsilicon. In fact, they are based on Si—O—Si chains that contain verystable bonds and are resistant to high temperature. However, theinventors have surprisingly discovered that it is necessary to usepolymers that do not contain silicon. The advantageous effects explainedbelow are obtained when the constituent elements of the polymers areselected from among carbon, hydrogen, oxygen or nitrogen. Duringheating, these polymers break down at a temperature below T_(γ) and arepartly combined with the oxygen of the furnace atmosphere. It would thenbe expected that the pigments of the paint, deprived of binder, would nolonger adhere to the substrate and would become disconnected. Theremight also be reason to fear that after heating, there would be a layeroriginating from the decomposition of the paint that would prevent thelater implementation of cataphoresis or resistance welding. However, theinventors have shown that surprisingly, these undesirable consequencesdo not occur under the conditions of the invention.

The nitrogen content of the polymerized layer 3 must be limited to 1%,preferably 0.5%, and very preferably 0.2%, under penalty of formingcompounds of the HCN type or excessive quantities of ammonia duringheating to the temperature necessary for stamping.

The content by weight of carbon pigments, expressed in relation to thepolymerized layer 3, is between 3 and 30%. Below 3%, the reduction ofthe heating cycle time is insufficient. Above 30%, the mixture has aviscosity unsuitable for application. In this range of contents, thepart obtained after hot stamping has practically no surface enrichmentin carbon, as will be shown below.

The carbon pigments can be in the form of graphite or activated carbon.The latter, which is obtained by a high temperature carbonization step,has an amorphous structure and a large specific surface area that givesit a high adsorbent power. The content by weight of activated carbon,expressed in relation to the deposited layer, must be less than 5% to besuitable for mixing with the polymer.

The blanks comprising the metallic pre-coating and the layer of polymercontaining the particles of carbon are heated in a furnace under anordinary atmosphere from the ambient temperature to a temperature T_(γ),conventionally in the neighborhood of 900° C., which makes thesubsequent hot stamping possible. During the heating, the carbon in thelayer remains present on the surface of the blank for the largest partof this heating step, i.e. its effect on the reflectivity is exertedover the majority of this step and it therefore contributes to reducevery significantly the duration of the step. Under the conditions of theinvention, the inventors have found that it gradually combines with theoxygen in the furnace during the heating and disappears almostcompletely when the blank reaches the temperature T_(γ). The inventorshave also found that the application of paint according to the inventiondoes not require a subsequent sandblasting treatment to eliminate apotential oxide layer, which could have an adverse effect on asubsequent painting by cataphoresis. The application of the paintaccording to the invention does not modify the suitability forresistance welding of the parts after hot stamping, so that it is notnecessary to modify the settings of the welding machines. In addition,as will be shown below, the method according to the invention makes itpossible to increase the resistance to delayed cracking of the hotstamped parts, on account of the reduction of the content of diffusiblehydrogen. The application of the paint according to the invention doesnot reduce the corrosion resistance of the hot stamped parts.

The invention can be implemented in one particular mode which isillustrated in FIG. 2, which schematically shows a welded blankcomprising two blanks 7 and 8 having respective thicknesses e₇ and e₈such that

$\frac{e_{7}}{e_{8}} > 1.$These two blanks comprise a steel substrate pre-coated with aluminum oraluminum alloy, wherein the pre-coating is identical on both blanks. Thewelded joint can be created by any appropriate method, in particular byarc welding or by laser welding. If a welded seam of this type is heatedfor hot stamping, the different thicknesses of the constituent partsresults in a different heating kinetic in the two parts, wherein theblank 7 is heated less rapidly than the thinner blank 8. That in turncan lead to different microstructures and different properties in thesubstrate and in the coating of the parts 7 and 8 after hot stamping. Incertain cases, it is not possible to determine satisfactory operatingconditions, such as the heating temperature and the hold time, to obtainthe desired properties in the different constituent zones of the weldedjoint.

The invention teaches that a layer of polymer described above isdeposited to obtain a polymerized layer containing 3 to 30% carbonpigments on the thicker blank 7. The thinner blank 8 does not have sucha layer on the aluminum or aluminum alloy pre-coating. Depending on thedesired uniformity of properties over the hot stamped part, it ispossible to deposit the layer over the entire blank 7 or only over aportion of it. The welded blank is then placed in a furnace. The priorapplication of the layer of paint makes it possible to increase theemissivity of the blank 7 and to reduce the difference in the heatingrate between the two blanks 7 and 8 resulting from their difference inthickness.

The inventors have shown that when the blanks are provided in such formthat

${2.6 \geq \frac{e_{7}}{e_{8}} \geq 2.2},$the duration of heating is practically the same in parts 7 and 8,because the application of the layer of paint according to the inventionmodifies the emissivity to compensate almost entirely for the effect ofthe difference between the thicknesses of blanks 7 and 8 on the heatingcycle, which guarantees excellent uniformity of the properties of thepart after hot stamping and press hardening.

The blanks 7 and 8 can be pre-coated, for example, with analuminum-silicon alloy comprising by weight 7-15% silicon, 2 to 4% iron,optionally between 15 and 30 ppm calcium, the remainder consisting ofaluminum and the unavoidable impurities resulting from processing. Underthese conditions, as illustrated schematically in FIG. 3, thepre-coating 2 comprises an intermetallic alloy layer 4 severalmicrometers thick comprising in the majority Fe₂Al₃, Fe₂Al₅ andFe_(x)Al_(y)Si_(z), in contact with the steel substrate 1. Thisintermetallic layer 4 is overlaid by a layer of metallic alloy Al—Si—Fe5. On the thicker blank 7, this layer 5 is itself overlaid by a layer ofpolymer 3 described above, containing 3 to 30% carbon pigments. Toprevent the formation of brittle intermetallic compounds in the moltenzone during welding, the layer of metallic alloy 5 is removed on theperiphery of the blanks, leaving the thin layer of intermetallic alloy 4in place. This local ablation can be carried out by any means, inparticular by melting and vaporization using a pulsed laser. Theinventors have shown that the presence of the polymer layer with thecarbon pigments does not interfere with the ablation, which can becarried out under satisfactory conditions of productivity. By way ofexample, the desired results can be obtained using a laser power of 50 Wto 1.5 kW, ablation rates on the order of 3 to 6 m/mn and a wavelengthof 300 to 1500 nm.

FIG. 3 illustrates one example where the layer of paint 3 and a layer ofmetallic alloy 5 have been removed on one edge of a pre-coated paintedblank. The intermetallic coating 4 is therefore exposed on the surface 6after this ablation. FIG. 3 illustrates an example where the ablationhas been carried out on a single surface of the blank. It is alsopossible to perform this ablation on both faces when it is desirable tominimize the quantity of aluminum introduced into the molten weldingmetal by remelting.

The blanks are welded along the edge where the ablation has beenperformed. The blanks are then heated, hot stamped and press hardened.

The inventors have shown that the method according to the inventionmakes it possible to fabricate hot stamped parts that have goodsuitability for spot welding and painting by cataphoresis, goodresistance to corrosion and to delayed cracking.

By way of non-restrictive examples, the following embodiments illustratethe advantages achieved by the invention.

EXAMPLE 1

Blanks 1 mm thick were provided made of steel having the followingcomposition in percent by weight: 0.228% C, 1.189% Mn, 0.014% P, 0.001%S, 0.275% Si, 0.028% Al, 0.034% Ti, 0.003% B, 0.177% Cr, the balancebeing iron and impurities resulting from processing. These blankscomprise a pre-coating 24 μm thick on each surface, containing 9% byweight silicon, 3% by weight iron, the balance being aluminum andunavoidable impurities. On some of these blanks, a layer was thendeposited by roll coating over the entirety of the two surfaces composedof polymer and carbon pigments, in aqueous phase, under the differentconditions indicated in the table below. The acrylic phenoxy resincontains less than 0.2% nitrogen on the deposited layer. The percent byweight of carbon pigments in these roll-coated layers is indicated inTable 1 below. The layers deposited were dried by passing through a kilnat 70° C. for 5 minutes.

TABLE 1 Test conditions Percent by Percent by weight of weight ofgraphite activated carbon carbon pigments, pigments expressed expressedin in Thickness of relation relation the layer Type of polymer of to theto the deposited the layer deposited layer after layer after afterdrying Test on the pre-coating drying (%) drying (%) (micrometers) I1Acrylic-phenoxy resin 5 — 15 I2 Acrylic-phenoxy resin — 15 15 I3Acrylic-phenoxy resin 1 12 15 I4 Acrylic-phenoxy resin 1 12 11 I5Acrylic-phenoxy resin 1 12 26 R1 Polysiloxane 0  0 30 R2 No polymercoating, — — — no carbon pigments (I = Invention, R = Reference)

Thermogravimetric analyses show that the majority of the acrylic resindecomposes at approximately 400° C.

Steel blanks prepared under the conditions indicated in the above tablewere heated from the ambient temperature to 900° C. in a furnace underan ordinary atmosphere, held at this temperature for one minute, thenhot stamped and temper-hardened by holding them in the stamping tool.The rapid cooling thus obtained convers a martensitic structure on thesteel substrate. The mechanical strength Rm is about 1500 MPa.

The thermal cycle causes an alloying of the iron of the substrate withthe coating, thereby creating intermetallic alloys containingessentially aluminum, iron and silicon.

In each of the above conditions, thermocouples were used to measure theduration of heating Δt₂₀ ⁹⁰⁰, i.e. the time that elapses between theinstant when the blank is at ambient temperature and when it reaches900° C. The results are presented in Table 2.

TABLE 2 Duration of heating from 20 to 900° C. Test Δt₂₀ ⁹⁰⁰ (s) I1 70I2 70 I3 70 I4 70 I5 70 R1 68 R2 165

The application of a polymerized layer comprising carbon pigments (testsI1 to I5 and R1) makes it possible to reduce the heating time by morethan 50% compared to the metallic pre-coating alone (test R2).

The average rate obtained during heating between 50 and 500° C. was alsomeasured on blanks prepared under the conditions I3 and R2 having athickness between 1 and 2 mm. Table 3 presents the results obtained.

TABLE 3 Heating rate between 50 and 500° C. V20-500° C. Test Thickness(mm) (° C./s) I3 1 31 1.5 22 2 16 R2 1 12 1.5 10 2 7

Under the conditions of the invention, it has therefore been shown thatit is possible to obtain a heating rate between 15 and 40° C./s between50 and 500° C. for the entire range of thicknesses, while this rateremains below 12° C./s under the reference conditions R2.

FIG. 5 illustrates the oxygen analyses by Glow Discharge OpticalSpectroscopy performed on blanks heated to 900° C. and then hardened.These analyses express the variation of the oxygen content in percent byweight as a function of the thickness starting from the surface of thepress-hardened parts. In relation to the reference tests R1(polysiloxane base coating) and R2 (metallic pre-coating withoutapplication of paint), the application of resin and carbon pigmentsaccording to the invention (I3) results in a reduction of the oxidelayer on the extreme surface. In the case of test I3, the average oxygencontent measured between 0 and 0.01 μm below the surface is 16.7%, whileit is 30.3% for test R2. This reduction in the average surface oxygencontent makes it possible to reduce the contact resistance, whichimproves the suitability for spot resistance welding. Without being tiedto a specific theory, it is thought that the deposition of the polymerlayer according to the invention to a certain extent protects theunderlying layer of aluminum alloy and reduces the formation of aluminaon the surface.

In the other tests I4 and I5, it has been found that the variation ofthe oxygen content as a function of the depth is very similar to thatillustrated for I3 in FIG. 5.

In the case of the test R1, the use of a polysiloxane base polymerresults in the formation of a thick oxide layer. The average oxygencontent measured between 0.1 and 0.2 μm below the surface is 18%, whileit is less than 10% under the conditions of the invention: 3.8% in thetest I3, 3% for the test I4, 4.8% for the test I5. In the case of thetest R1, to perform subsequent painting by cataphoresis, it is necessaryto remove the oxide layer by expensive sandblasting or shot blastingtreatments, while these treatments are not necessary in the case of theinvention because the oxide layer has a significantly lower thickness.

In the tests I3-I5 according to the invention, the surface oxygencontent after press hardening is relatively independent of the thicknessof the polymerized layer deposited on the pre-coating, as shown in thetable below.

TABLE 4 Characteristics of the oxygen content on the surface as afunction of the thickness of the polymer deposit on the pre-coatingAverage oxygen Average oxygen content between 0 content betweenThickness of the and 0.01 0.1 and 0.2 deposited layer micrometersmicrometers after drying below the surface below the surface Test(micrometers) (%) (%) I4 11 17.5 3 I3 15 16.6 3.8 I5 26 14.4 4.8

This means that the initial step of depositing the polymer layer withthe particles of carbon can be carried out with a certain tolerance interms of thickness and therefore does not require the implementation ofspecific expensive application methods.

It will be observed in FIG. 6 that the deposition of carbon pigmentswith the polymer under the conditions of the invention (tests I3 and I5)does not cause significant surface enrichment in carbon compared to thereference situation R2. Contrary to what would have been expected, theinventors have shown that the addition of carbon pigments even reducesthe carbon content on the extreme surface after the press hardeningtreatment. This indicates that a reaction of the carbon with oxygen inthe atmosphere occurs almost completely during the heating phase of theblank in the furnace.

Under the conditions of the invention, tests interrupted at differenttemperatures during the heating show that the carbon remains present onthe surface of the blank for the majority of this step, i.e. that itseffect on the reflectivity occurs directly during a very large part ofthe heating cycle. But, as indicated above, the gradual combination ofthe atmospheric oxygen with the carbon results in an almost completedisappearance of the latter element when the blank reaches thetemperature of 900° C.

In the case of a deposit laid down under the reference conditions (R1),FIG. 7 shows the variations of the carbon, oxygen and silicon content byweight measured on the parts obtained by heating to 900° C., holding atthis temperature for one minute, followed by hot stamping and presshardening. In addition to a higher oxygen content than in the testsaccording to the invention I3-I5, there is a significant increase in thesurface content of silicon, which is present in the form of oxide whichmodifies the suitability for resistance welding on account of the sharpincrease of the contact resistance, which is greater than 1.5 milliohms.

The suitability for spot resistance welding of parts created accordingto the conditions I2 and R2 was evaluated by executing spot welds undera welding force of 350 daN. The width of the range of weldability wasevaluated by the difference between the minimum intensity I_(min) makingit possible to obtain a spot diameter of 6 mm associated with asatisfactory mechanical strength, and the maximum intensity I_(max)beyond which there is an expulsion of liquid metal during the welding.The width of the weldability range (I_(max)−I_(min)) is approximately1500 A, equivalent for the conditions I2 and R2. Likewise, it has beenfound that the results of crosswise tensile tests on the spot welds areidentical. For a welding intensity I_(min), the mechanical strength isequal to 3370 N (condition R2) and 3300 N (condition I2). For a weldingintensity I_(max), the mechanical strength is equal to 4290 N (conditionR2) and 4127 (condition I2). Therefore, the application of polymer andcarbon particles according to the invention does not modify thesuitability for spot welding. The invention can be implemented withoutmodifying the settings of the welding machines. It is possible to weld asheet pre-coated with aluminum or aluminum alloy with a deposit ofpolymer and carbon according to the invention and a sheet that has onlybeen pre-coated, in the assurance that the welding conditions will beperfectly adequate for these two types of sheets.

The surfaces of parts hot stamped and hardened under conditions I1-3 andR2 were observed in terms of the zenith under the Scanning ElectronMicroscope. Under the reference condition (R2, FIG. 8), the surfaceroughness is significant, which guarantees good paintability by latercataphoresis.

FIG. 9 shows that the surface roughness of the part fabricated under thecondition of the invention (I2) is similar. Identical observations wereconducted for conditions I1 and I3. Because it was noted above, that thesurface of the parts fabricated according to the invention is notenriched in carbon, that guarantees that the suitability forcataphoresis is not reduced by the prior application of the polymer andcarbon pigments.

EXAMPLE 2

The resistance to different forms of corrosion of hot stamped and presshardened parts fabricated was evaluated according to the conditions I2(AlSi pre-coating and painting according to the invention) and R2 (AlSipre-coating alone) from Table 1.

The resistance to cosmetic corrosion was determined under the followingconditions: scratches of different depths were made, affecting only thecoating (condition A) or also affecting the substrate (condition B) ofhot stamped parts. These parts were subjected to cycles of temperatureand moisture in a saline mist for six weeks under the conditionsdescribed in the “New VDA Test 233-102”, which is in itself known. Thewidth of blistering at the level of the scratch was then measured. Theresults are presented in Table 5.

TABLE 5 Results of cosmetic corrosion Width of blistering (mm) Width ofblistering (mm) Condition A Condition B I2 2.7 4 R2 2.6 4.2

Compared to the reference test R2, it was found that the application ofpaint according to the invention does not reduce the resistance tocosmetic corrosion.

The resistance to perforating corrosion was evaluated by tests conductedover 12 weeks under the “New VDA” test conditions indicated above. Theweight losses measured for the parts fabricated under conditions I2 andR2 are as follows:

TABLE 6 Results of cosmetic corrosion Weight loss (g/m²) I2 170 R2 180

Compared to the reference test R2, the application of the paintaccording to the invention does not reduce resistance to perforatingcorrosion.

1 mm parts hot stamped and fabricated according to conditions I2 and R2were subjected to painting by cataphoresis. The adherence of thiscataphoresis layer after scratches in a checkered pattern was measured,followed by immersion in water at 50° C. for 10 days. It was found thatthe application of the paint according to the invention does not reducethe adherence of the cataphoresis layer.

EXAMPLE 3

Blanks made of 22MnB5 steel 1, 5 and 2 mm thick comprising on both theirsides a pre-coating 23 μm thick containing 9% Si and 3% Fe, the balancebeing aluminum and unavoidable impurities, were acquired. On some of theblanks, a layer composed of polymer and carbon pigments was deposited byroll coating over the entirety of the two principal surfaces underconditions I2 according to the invention indicated in Table 1. The otherblanks were not painted (condition R).

The blanks were heated to 900° C., held at this temperature for oneminute, then hot stamped and hardened by holding them in the stampingtool. The diffusible hydrogen content was measured using a thermaldesorption analysis method, which is in itself known. The diffusiblehydrogen content of these blanks is presented in Table 7.

TABLE 7 Diffusible hydrogen content Thickness of Diffusible hydrogenCoating the flan (mm) content (ppm) I2 1.5 0.15 R 1.5 0.21 I2 2 0.17 R 20.25

The deposit of the specific paint according to the invention makes itpossible to reduce very significantly the content of diffusiblehydrogen. Without being bound by a theory, the inventors think that theapplication of the deposit according to the invention reduces the lengthof time during which the hydrogen can be adsorbed during the heatingstep prior to stamping. The invention therefore makes it possible toreduce significantly the sensitivity to delayed cracking of the hotstamped and hardened parts. The implementation of the inventiontherefore makes it possible to utilize steels that contain higher levelsof alloy elements and results in a higher mechanical strength after hotstamping, all without increased risk with reference to delayed cracking.

EXAMPLE 4

Blanks made of 22MnB5 steel 1, 2 and 2.5 mm thick comprising on boththeir sides a pre-coating 23 μm thick containing 9% Si and 3% Fe, thebalance being aluminum and unavoidable impurities, were acquired. Thepre-coating is constituted by a thin layer of intermetallic alloy, themajority of which consists of Fe₂Al₃, Fe₂Al₅ and Fe_(x)Al_(y)Si_(z),approximately 4 μm thick in contact with the steel substrate. Thisintermetallic layer is overlaid by a layer of Al—Si metallic alloy 19 μmthick.

On some of the blanks a layer composed of polymer and carbon pigmentswas deposited by roll coating over the entirety of the two principalsurfaces under the conditions I2 indicated in Table 1.

These blanks were heated to 900° C. The thermal cycles measured bythermocouples made it possible to determine the thermal emissivity. Forthe sheets painted according to the invention, the thermal emissivitydecreases during the heating cycle from approximately 0.6 to 0.3. Forthe unpainted reference sheets, the emissivity decreases fromapproximately 0.2 to 0.1 during the heating cycle.

With reference to the schematic FIG. 2, blanks were assembled by laserwelding, wherein these blanks were two blanks of different thicknesses.The thinner of the blanks, identified as 8, with a thickness e₈, isconstituted by a sheet pre-coated with the above aluminum alloy. Thethicker blank, identified as 7, with a thickness e₇, is constituted by asheet pre-coated with the same aluminum alloy and a polymerized layeraccording to condition I2 above. To prevent the formation ofintermetallic compounds in the zone melted during welding, a pulsedlaser was used to remove the metallic Al—Si—Fe alloy coating by ablationon both surfaces over a width of 1.1 mm from the periphery of theblanks, leaving the thin layer of intermetallic alloy in place. In thecase of unpainted pre-coated blanks, only the layer of metallic alloywas removed; in the case of pre-coated blanks with a polymerized layer,the layer of metallic alloy as well as the polymerized layer wereremoved over the width indicated above. An ablation rate of 3 m/mn makesit possible to obtain the desired results.

These welded blanks were then heated to 900° C. by measuring thetemperature using thermocouples placed in each of the two parts 7 and 8of the welded blanks (blanks with thicknesses e₇ and e₈). The heatingtime Δt₂₀ ⁹⁰⁰ in each of parts 7 and 8 was thereby determined as well asthe temperature difference between these two parts at every instant ofthe heating. The maximum temperature difference during the heating cycleΔΘ₇ ⁸, as well as Δt₂₀ ⁹⁰⁰ are presented in Table 8. The welded blanksare then hot stamped and press hardened.

TABLE 8 e₇ (mm) blank e₈ (mm) without blank with Test ID polymerizedlayer polymerized layer $\frac{e_{7}}{e_{8}}$ Δ t₂₀ ⁹⁰⁰ (7) (s) Δ t₂₀⁹⁰⁰ (8) (s) Δ Θ₇ ⁸ (° C.) I4 2 1 2 160 170 44 I5 2.5 1 2.5 175 170 2

By comparison, Table 9 presents the results obtained during the heatingof a welded blank constituted by two blanks pre-coated with Al—Si alloy,unpainted, with respective thicknesses of 2 mm and 1 mm.

TABLE 9 e₇ (mm) blank e₈ (mm) Test ID not painted blank not painted$\frac{e_{7}}{e_{8}}$ Δ t₂₀ ⁹⁰⁰ (7) (s) Δ t₂₀ ⁹⁰⁰ (8) (s) Δ Θ₇ ⁸, (° C.)R3 2 1 2 360 170 155

Under the conditions of the invention (test I4 and I5), the heating timeis very similar in the two parts 7 and 8 that make up the welded joint.This makes it possible to ensure that the microstructures of the steelsubstrate after austenitization and of the coating obtained byinterdiffusion will be very similar in the parts 7 and 8 of the weldedjoint. By comparison, the reference test R3 results in a situation inwhich the thicker part of the welded blank is heated to 900° C. muchmore slowly than the thin part. If is therefore necessary for the thinpart of the welded joint to be held at 900° C. for 190 s so that thethick part reaches the temperature of 900° C., which can lead to anundesirable austenitic grain growth in the steel substrate of thethinner part, or to an excessive interdiffusion between the pre-coatingand the substrate in this part. The method according to the inventionmakes it possible to prevent these problems.

In test I5, where the ratio

$\frac{e_{7}}{e_{8}}$is equal to 2.5, the temperature difference between the two parts of thewelded joint at any point in the heating cycle is particularly low, lessthan 2° C., while it is equal to 44° C. in test I4

$\left( {\frac{e_{7}}{e_{8}} = 2} \right).$This preferential mode in which the thickness ratio is between 2.2 and2.6 will be selected when the objective is the greatest possible thermaluniformity during the heating of welded blanks.

Therefore the invention makes the fabrication of hot stamped piecespossible under conditions of increased productivity, exhibiting a goodsuitability for spot welding and painting by cataphoresis, highresistance to corrosion and to delayed cracking. These parts can beadvantageously used as structural parts or reinforcements in the fieldof automobile construction.

What is claimed is:
 1. A sheet or pre-coated blank comprising: a steelsubstrate for heat treatment having; a pre-coating on at least one faceof the steel substrate, the pre-coating including at least one layer ofaluminum or aluminum alloy; a polymerized layer directly contacting atleast a part of the pre-coating, the polymerized layer having athickness from 2 μm to 30 μm, the polymerized layer comprising a polymerresin and carbon pigments, wherein the polymer resin consists of anacrylic resin or an epoxy resin, wherein the polymer resin does notcontain silicon, wherein the polymerized layer has a nitrogen content ofless than 1% by weight and wherein carbon pigments are present in thepolymerized layer in a quantity from 3 to 30% by weight.
 2. The sheet orpre-coated blank according to claim 1, wherein the polymerized layer isobtained from a resin in a form of a dispersion or emulsion in aqueousphase.
 3. The sheet or pre-coated blank according to claim 2, whereinthe polymerized layer is obtained from an acrylic resin.
 4. The sheet orpre-coated blank according to claim 1, wherein the polymerized layer isobtained from a resin in the form of solution in a non-aqueous solvent.5. The sheet or pre-coated blank according to claim 1, wherein thepolymerized layer is a film roll bonded to the substrate.
 6. The sheetor pre-coated blank according to claim 1, wherein the carbon pigmentsinclude activated carbon.
 7. The sheet or pre-coated blank according toclaim 6, wherein a quantity of activated carbon in the polymerized layeris less than 5% by weight.
 8. The sheet or pre-coated blank according toclaim 1, wherein the carbon pigments include graphite.
 9. The sheet orpre-coated blank according to claim 1, wherein the layer of aluminum oraluminum alloy is more than 50% of a thickness of the pre-coating. 10.The sheet or pre-coated blank according to claim 1, wherein thepre-coating includes a layer of intermetallic alloy in contact with thesteel substrate and overlaid by the aluminum or aluminum alloy layer,and on at least one pre-coated face of the sheet, the polymerized layerand the aluminum or aluminum alloy layer are not present in a zone, thezone being located on a periphery of the sheet or blank.
 11. The sheetor pre-coated blank of claim 1, wherein the polymer in the polymerizedlayer consists of an acrylic resin.
 12. The sheet or pre-coated blank ofclaim 1, wherein the polymer in the polymerized layer consists of anepoxy resin.